Mercuri alkyl phenol derivatives



Patented Nov. 22, 1938 U I D STATES PATENT- OFFICE 1 MERCURI ALnYnPnE oL nnmvnrlvns Walter G. Ghristiansen, Glen Ridge, N. J., and

7 Eugene Moness, Long Island City, N. Y.;'as-

. signorst'o E. It; Squibb & Sons, New York,'N. Y., a corporation of New York No Drawing.

4 Claims.

This invention relates to, and has for its object the provision of, certain mercuri alkyl phenol derivatives and an advantageous method of preparing them.

The compounds of this invention are mercuri alkyl phenol derivatives of the group consisting o en 7 j *0 and g anion-Hg- EXAMPLES Anhydro-mercu'rz' Z-chloro 4-tertiary-butyl v phenol 5.25 g. 2-chloro 4-tertiary-butyl phenol is dissolved in 36 cc. methyl alcohol, and while the solution is refluxed on a steam-bath, 9 g. mercuric acetate dissolved in 26 cc. water slightly acidulated With acetic acid is added rapid-drop- Wise with mechanical stirring. ,After two hours of refluxing, a test for divalentmercury being negativeand white crystals having formed, the mixture is' filtered; the residue, upon being washed successively with methyl alcohol, water, and methyl alcohol, and dried, is found to be soluble in dilute alkali. I

2-or-4-chloro 3,6-dz'methyl phenol s Anhydro-mercuri 4 g. chloro, 3fi-dimethyl-phenol is dissolved in Anhydro-mercuri Application September 13, 1934, Serial No. 743,840 1 I 20 cc. methylalcohol, and while the solution is refluxed on a steam-bath, 8 g. mercuric acetate dissolved in'20 ccfwaterslightly aciclulated with acetic acid is added rapid-dropwise with mechanical stirring. After one and one-half hours of refluxing, a' test for divalent mercury being negative and heavy white crystals having formed, the residue is filteredout and washed as in the first example. l v

Anhydro-mercuri' 2-or-4-chloro, 3,5-dimethyl 1. phenol or Hg- HaC CH3 'Ifl1 is compound is prepared precisely in accordance: with the preceding example except that chloro 3,5-dimethyl phenol is substituted for chloro 3,6-dimethyl phenol.

2-chloro 4-tertiary-amyl phenol 4.02 g. 2-chloro fl-tertiary-amyl phenol is dissolved in 40 cc. methyl alcohol, and while the solution is refluxed on a steam-bath, 6.40 g. mercuric acetate dissolved in 30 cc. slightly acidulatedwater is added rapid-dropwise with mechanical stirring. After seven hours of refluxing, atest for divalent mercury being nega- ;tive, the desired compound is obtained in the form ofwhit'e crystals by filtering, washing, and drying as in the foregoing examples- Hydroxymercnri 3-methyl 4-chloro phenol 7.25 g. 3-methyl 4chloro phenol is dissolved.

in 50 cc. methyl alcohol, and while the solution is refluxed on a steam-bath, 16 g. mercuric acetate dissolvedin 50 cc water is added dropwise withmechanical stirring; ,After five hours of V refluxing, a test 'for divalent mercury being negative, the desired compound is obtained in the form of grayish-white crystals by filtering, Washing, and drying as in the foregoing examples. Purification may be effected by dissolving in dilute alkali, filtering, and precipitating either by treating the filtrate with dilute acetic acid or by saturating the filtrate with carbon dioxide.

Acetoxymercuri s-methyl 4-chloro fi-isopropyl phenol (CHQQCH CHaC O OHgo1 9.25 g. 3-methyl 4-chloro 6-isopropy1 phenol is dissolved in 50 cc..methyl alcohol, and while the solution is refluxed on a steam-bath, 14.7 g. mercuric acetate dissolved in 50 cc. water slightly acidulated with acetic acid is added. After five hours of refluxing, a test for divalent mercury being negative, the reaction mixture is filtered, Washed, and dried as in the foregoing examples, yielding the desired compound in the form of White crystals.

Acetoxymercuri 2-chloro 4-pr0pyl phenol Hydromy mew-curt 3-z'sopropyl 4-chloro 6-methyl phenol 113C HOHg- CH(CH3)2 A solution of 8 g. 3-isopropyl 4-chloro G-methyl phenol in 150 cc. ethyl alcohol is treated in the manner of the foregoing examples with 12.5 g. mercuric acetate in 45 cc. water. After twelve hours of refluxing, a test for divalent mercury being slightly positive and some crystals having formed, the mixture is filtered. The filtrate is made strongly alkaline with dilute alkali, and the grayish muddy precipitate is filtered out. The dark-red alkaline filtrate is acidified with dilute acetic acid, and the reddish-brown precipitate, the desired compound, is filtered 01f, washed with water and then with alcohol, and dried to a reddish powder, which gives a dark-red solution with dilute alkali.

Acetoxymercuri 1,3-dihydroccy 4-butyl 6-chloro benzene 4H9 0.9 g; 1,3-dihydroxy 4-butyl 6-chloro benzene is dissolved in 10 cc. ethyl alcohol, and while the solution is refluxed, 1.5 g. mercuric acetate dissolved inlO cc. water is added. After two hours of refluxing, a test for divalent mercury being negative, and the reaction mixture being brownish and turbid, the alcohol is evaporated off and the mass dissolved in dilute alkali. Finely divided reduced mercury is filtered out. Precipitation is effected by means of acetic acid. For purification, the precipitate is dissolved in boiling alcohol, and a slight residue filtered out. Diluting the alcoholic solution with water yields the desired compound as a pinkish precipitate.

Acetoxymercuri Z-nitro 4-tertiary-butyl phenol N09 CHaC 0 011g- 5.14 g. 2-nitro 4-tertiary-butyl phenol is dissolved in 50 cc. methyl alcohol, and while the solution is refluxed on a steam-bath, 8 .g. mercuric acetate dissolved in 3000. water slightly acidulated with acetic acid is added. After five hours of refluxing, a test for divalent mercury being negative, the precipitate, which is the desired compound, is filtered off, washed successively with a little methyl alcohol, water, and:

methyl alcohol, and dried to yellow-orange crystals, which give an orange solution in dilute alkali.

Acetoxymercuri 2-nit1'o-3,6-dimethyl phenol H36 N02 onloo OHg- 2.19 g. 2-nitro 3,6-dimethyl phenol is dissolved in 13 cc. methyl alcohol, and while the solution is refluxed on a steam-bath, 3.93 g. mercuric acetate dissolved in 13 cc. water slightly acidulated with acetic acid is added. After seven hours of refluxing, a test for divalent mercury being negative, the reddish-brown crystal precipitate, the desired compound, is filtered, washed, and dried as in the preceding example, and is found to give a light-red solution with dilute alkali.

Acetoazymercnri Z-nitro 4-tertiary-amyl phenol NO; CHaCO OHg- Hydrorymercnrz' Z-nitro 4-p1opyl phenol NO; HOHg- 2.3 g. 2-nitro 4-propyl phenol is dissolved in 25 cc.

Acetoxymercw'i 3-methiyl 4-mtro 6-z'sopropyl. phenol (CHahCH cmooon 7 N02 2.5 g. B-methyl 4-nitro fi-isopropyl phenol is dissolved in 13 cc. methyl alcohol, and while the solution is refluxed on a steam-bath, 4 g. mercuric acetate dissolved in 12 cc. water slightly acidulated with acetic acid is added. After seven hours of refluxing, a test for divalent mercury being negative, the crystalline yellowish precipitate, the desired compound,'is isolated as in the preceding examples, and found to give an orange solution with dilute alkali. 7

Among the numerous other compounds that 'may be prepared in accordance with the invention are the following (the chloro, the cyano, the thiocyano, the nitrato, and the hydroxy compounds being formed by treating solutions of the acetoxy compound with. respectively, the chloride, the cyanide, the, thiocyanide, the nitrate, and the hydroxide, of an alkali metal).

Chloromercuri 2-chlor0 4-tertiary-butyl phenol.

Cyanomercuri 2-chloro 4-tertiary-butyl phenol.

Anhydro-mercuri 2-bromo 4-tertiary-butyl phenol.

Anhydro-mercuri 2-chloro 4-normal-butyl phenol.

Anhydro-mercuri 2-chloro 4-normal-amyl phenol.

Acetoxymercuri 1,3-dihydroxy 4-amyl 6-chloro benzene. Acetoxymercuri 1,3-dihydroxy 4-hexyl 6-chloro benzene. Chloromercuri 2-chloro 4-propyl phenol. Acetoxymercuri 2-bromo 4-propyl phenol. Nitratomercuri 2-nitro 4- normal-buty1 phenol. Thiooyanomercuri 2-nitro 4-normal-amyl phenol. Chloromercuri 2-nitro 4-propyl phenol.

Acetoxymercuri 2-propyl 4-chloro phenol.

Hydroxymercuri 2-propyl 4-nitro phenol.

It is to be understood that the foregoing ex amples are merely illustrative and by no means limitative of the invention, which may be variously otherwise embodied within the scope of the appended claims.

We claim:

1. Anhydro-mercuri 2-chloro 4-tertiary-buty phenol.

2. Acetoxymercuri 2 nitro 4 tertiary-butyl phenol.

3. Mercuri' alkyl phenol derivatives of the group consisting of wherein Z represents a member of the group consisting of halogen and nitro; and R represents a branched-chain alkyl.

4. Acetoxymercuri phenol.

2 nitro 4 tertiary-amyl WALTER G. CHRISTIANSEN. EUGENE MONESS. 

